The subject invention provides compositions of and methods of using carbo and heterocyclic spiro compounds as donor materials for organic photovoltaic (OPV) devices. In preferred embodiments, spiro compounds comprising triarylamine and derivatives thereof demonstrate effective hole-transporting properties in OPV devices, achieving up to 5.46% of power conversion efficiency. Advantageously, preferred compounds provided herein are thermally stable and volatile enough to form thin films for the photoactive layer of an OPV device by vacuum deposition or by spin-coating.